US7088490B2 - Electrochromic mirror having variable reflectivity - Google Patents

Electrochromic mirror having variable reflectivity Download PDF

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Publication number
US7088490B2
US7088490B2 US10/867,778 US86777804A US7088490B2 US 7088490 B2 US7088490 B2 US 7088490B2 US 86777804 A US86777804 A US 86777804A US 7088490 B2 US7088490 B2 US 7088490B2
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Prior art keywords
film
electrochromic
electrolytic solution
light reflecting
electrochromic mirror
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Expired - Lifetime
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US10/867,778
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US20050002080A1 (en
Inventor
Junichi Nakaho
Masao Ayabe
Masaharu Hattori
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Tokai Rika Co Ltd
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Tokai Rika Co Ltd
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Assigned to KABUSHIKI KAISHA TOKAI-RIKA-DENKI-SEISAKUSHO reassignment KABUSHIKI KAISHA TOKAI-RIKA-DENKI-SEISAKUSHO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AYABE, MASAO, HATTORI, MASAHARU, NAKAHO, JUNICHI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/02—Rear-view mirror arrangements
    • B60R1/08—Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
    • B60R1/083—Anti-glare mirrors, e.g. "day-night" mirrors
    • B60R1/088—Anti-glare mirrors, e.g. "day-night" mirrors using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices

Definitions

  • the present invention relates to a rearview mirror for indoor or outdoor use which is applied to a vehicle such as a car, and more particularly, to an electrochromic mirror in which the reflectivity can be changed by applying voltage.
  • an “electrochromic mirror” is known (for instance, see Japanese Utility Model Application Publication (JP-Y) No. 62-2587).
  • An electrochromic mirror may be used as a rearview mirror for a vehicle such as a car and can electrically change the reflectivity so as to reduce the glare of the headlight of a following car at night.
  • a transparent electrode 104 a thin film made of iridium hydroxide (Ir(OH) 3 ) 106 , a thin film made of tantalum pentoxide (Ta 2 O 5 ) 108 , a thin film made of tungsten trioxide (WO 3 ) 110 , and an aluminum (Al) electrode 112 are sequentially laminated on the back surface of a glass substrate 102 by vacuum deposition or the like.
  • a glass plate 114 for protecting the thin films is adhered to the aluminum (Al) electrode 112 or the like by a sealant (adhesive) 116 .
  • the thin film made of iridium hydroxide (Ir(OH) 3 ) 106 and the thin film made of tungsten trioxide (WO 3 ) 110 react to be colored, and the reflectivity of the electrochromic mirror 100 is changed (see arrow B shown in FIG. 2 ).
  • an electrochromic mirror in which the reflectivity is changed by the coloring reaction of a so-called “electrochromic solution” which is a solution that is electrically colored is known (for instance, see Japanese Patent No. 2672083).
  • an electrochromic mirror 200 disclosed in Japanese Patent No. 2672083, two glass substrates 202 and 204 are arranged in parallel at a proper interval, and transparent electrode films 206 are respectively formed on the inner surfaces of the glass substrates 202 and 204 .
  • An electrochromic solution 210 is enclosed in a cell sealed by a sealant 208 between the transparent electrode films 206 .
  • a reflecting film 212 and a protective film 214 are formed on the back surface of the glass substrate 204 (the surface at the lower side in FIG. 3 ).
  • a voltage is applied between the transparent electrode films 206 by a power supply 216 , the electrochromic solution 210 is colored, and the reflectivity of the electrochromic mirror 200 is changed.
  • a first aspect of the present invention provides an electrochromic mirror having: a transparent substrate; a transparent electrode film which is formed on the transparent substrate and has conductivity; an electrochromic film which is formed on the transparent electrode film and can be colored by reduction; a light reflecting film which is formed on the electrochromic film and which hydrogen atoms can permeate; a support substrate which has a conductive part having conductivity formed on at least one surface thereof; and an electrolytic solution containing at least hydrogen ions, and neutral molecules or negative ions which can be oxidized, wherein the transparent substrate is located close to the support substrate such that the conductive part faces the light reflecting film, and the electrolytic solution is enclosed between the light reflecting film and the conductive part.
  • the transparent electrode film having conductivity is formed on the back surface of the transparent substrate, and the electrochromic film which can be colored by reduction is formed on the transparent electrode film.
  • the light reflecting film which hydrogen atoms can permeate is formed on the electrochromic film.
  • the electrochromic film is formed between the transparent electrode film and the light reflecting film.
  • the support substrate is located close to the back surface of the transparent substrate, and the light reflecting film faces the conductive part of the support substrate.
  • the electrolytic solution is enclosed between the light reflecting film and the conductive part of the substrate.
  • the electrolytic solution contains at least hydrogen ions, and neutral molecules or negative ions which can be oxidized.
  • the hydrogen ions contained in the electrolytic solution move toward the light reflecting film side of the transparent substrate, and the hydrogen ions are changed into hydrogen atoms.
  • the hydrogen atoms permeate the light reflecting film, and move toward the electrochromic film. Therefore, the following reduction reaction occurs in the electrochromic film.
  • H + is a hydrogen ion
  • MO is the material of an electrochromic film
  • e ⁇ is an electron
  • the electrolytic solution contains the neutral molecules or the negative ions which can be oxidized, and thereby the above reduction reaction of the electrochromic film is guaranteed.
  • the electrolytic solution contains the neutral molecules which can be oxidized and the neutral molecule is A
  • the following oxidation reaction occurs near the conductive part of the support substrate to which a positive voltage is applied in the electrolytic solution.
  • the electrolytic solution contains the negative ions which can be oxidized and the negative ion is B
  • the following oxidation reaction occurs near the conductive part of the support substrate to which a positive voltage is applied in the electrolytic solution.
  • the whole reaction is represented by the following formula (4).
  • the whole reaction is represented by the following formula (5).
  • the electrochromic film is colored by reduction.
  • the electrolytic solution contains the negative ions so as to match the formula (1) with the formula (2).
  • the electrolytic solution may not be colored by the reaction in the electrolytic solution.
  • the electrochromic mirror has a simple structure in which the transparent electrode film, the electrochromic film and the light reflecting film (three films) are formed on the back surface of the transparent substrate.
  • the film quality and film thickness or the like of each film do not easily influence performance. Therefore, the electrochromic mirror is easily manufactured at a low cost.
  • the electrochromic film is formed between the transparent electrode film to which a negative voltage is applied and the light reflecting film, hydrogen ions are compulsorily drawn into the electrochromic film. As a result, the response of the reduction coloring of the electrochromic film is improved.
  • the material of the electrochromic film such as tungsten trioxide may be dissolved little by little in the electrolytic solution.
  • the electrolytic solution can be selected in a wide range.
  • the electrochromic mirror of the first aspect can be easily manufactured at a low cost.
  • a second aspect of the invention provides an electrochromic mirror having: a transparent substrate; a transparent electrode film which is formed on the transparent substrate and has conductivity; an electrochromic film which is formed on the transparent electrode film and can be colored by reduction; a light reflecting film which is formed on the electrochromic film and which lithium atoms can permeate; a support substrate which has a conductive part having conductivity formed on at least one surface thereof; and an electrolytic solution containing at least lithium ions, and neutral molecules or negative ions which can be oxidized, wherein the transparent substrate is located close to the support substrate such that the conductive part faces the light reflecting film, and the electrolytic solution is enclosed between the light reflecting film and the conductive part.
  • the transparent electrode film having conductivity is formed on the back surface of the transparent substrate, and the electrochromic film which can be colored by reduction is formed on the transparent electrode film.
  • the light reflecting film which lithium atoms can permeate is formed on the electrochromic film.
  • the electrochromic film is formed between the transparent electrode film and the light reflecting film.
  • the support substrate is located close to the back surface of the transparent substrate, and the light reflecting film faces the conductive part of the substrate.
  • the electrolytic solution is enclosed between the light reflecting film and the conductive part of the substrate.
  • the electrolytic solution contains at least lithium ions and neutral molecules or negative ions which can be oxidized.
  • the lithium ions contained in the electrolytic solution move toward the light reflecting film side of the transparent substrate, and the lithium ions are changed into lithium atoms.
  • the lithium atoms permeate the light reflecting film, and move toward the electrochromic film. Therefore, the following reduction reaction occurs in the electrochromic film.
  • Li + is a lithium ion
  • MO is the material of an electrochromic film
  • e ⁇ is an electron
  • the electrolytic solution contains the neutral molecules or the negative ions which can be oxidized, and thereby the above reduction reaction of the electrochromic film is guaranteed.
  • the electrolytic solution contains the neutral molecules which can be oxidized and the neutral molecule is A
  • the following oxidation reaction occurs near the conductive part of the support substrate to which a positive voltage is applied in the electrolytic solution.
  • the electrolytic solution contains the negative ions which can be oxidized and the negative ion is B
  • the following oxidation reaction occurs near the conductive part of the support substrate to which a positive voltage is applied in the electrolytic solution.
  • the electrochromic film is colored by reduction.
  • the electrolytic solution contains the negative ions so as to match the formula (6) with the formula (7).
  • the electrolytic solution may not be colored by the reaction in the electrolytic solution.
  • the electrochromic mirror has a simple structure in which the transparent electrode film, the electrochromic film and the light reflecting film (three films) are formed on the back surface of the transparent substrate.
  • the film quality and film thickness or the like of each film do not easily influence performance. Therefore, the electrochromic mirror is easily manufactured at a low cost.
  • the electrochromic film is formed between the transparent electrode film to which a negative voltage is applied and the light reflecting film, lithium ions are compulsorily drawn into the electrochromic film. As a result, the response of the reduction coloring of the electrochromic film is improved.
  • the material of the electrochromic film such as tungsten trioxide may be dissolved little by little in the electrolytic solution.
  • the electrolytic solution can be selected in a wide range.
  • the electrochromic mirror of the second aspect can be easily manufactured at a low cost.
  • the electrochromic mirror of the invention can be easily manufactured at a low cost. In addition, no double images occur, and the electrochromic mirror has a simple structure and high performance.
  • FIG. 1 is a cross-sectional view showing the constructions of the electrochromic mirrors of first-fourth embodiments of the invention.
  • FIG. 2 is a cross-sectional view showing the construction of a conventional electrochromic mirror.
  • FIG. 3 is a cross-sectional view showing the construction of another conventional electrochromic mirror.
  • FIG. 1 is a cross-sectional view of the construction of the electrochromic mirror 10 of a first embodiment of the invention.
  • the electrochromic mirror 10 has a glass substrate 12 which is a transparent substrate.
  • a transparent electrode film 14 is formed in the form of a thin film on the back surface of the glass substrate 12 by vacuum deposition or the like (the surface at the lower side in FIG. 1 ).
  • the transparent electrode film 14 is a so-called “ITO film” made of a mixture of indium oxide and tin oxide in the first embodiment.
  • An electrochromic film 16 which can be colored by reduction is formed in the form of a thin film on the transparent electrode film 14 by vacuum deposition or the like.
  • the electrochromic film 16 is made of tungsten trioxide (WO 3 ) in the first embodiment.
  • a light reflecting film 18 is formed in the form of a thin film on the electrochromic film 16 by vacuum deposition or the like.
  • the light reflecting film 18 is made of rhodium in the first embodiment.
  • the electrochromic film 16 and the light reflecting film 18 are not formed at both end portions in the width direction of the glass substrate 12 , (at both end portions in the horizontal direction in FIG. 1 ), and only the transparent electrode film 14 is formed there.
  • a substrate (support substrate) 20 is disposed close to the back surface of the glass substrate 12 .
  • the substrate 20 is composed of a glass support 22 and an electrode film 24 , which is a conductive part, formed in the form of a thin film on one surface of the glass support 22 by means such as vacuum deposition. End portions on the electrode film 24 side of the substrate 20 are adhered to the transparent electrode film 14 by a sealant 26 such that the electrode film 24 faces the light reflecting film 18 .
  • the electrode film 24 is made of a metal such as chrome in the first embodiment.
  • a space sealed by a sealant 26 is formed between the light reflecting film 18 and the electrode films 24 of the substrate 20 , and an electrolytic solution 28 is enclosed in the space.
  • the electrolytic solution 28 contains propylene carbonate as a solvent, sulfuric acid (H 2 SO 4 ) as a hydrogen ion agent, and ferrocene (Fe(C 5 H 5 ) 2 ) which is a neutral material as a redox agent in the first embodiment.
  • a power supply 30 is electrically connected to the transparent electrode film 14 and the electrode film 24 of the substrate 20 via wiring 32 .
  • the power supply 30 has a direct-current power supply 34 and a switch 36 . In the state that the switch 36 is turned on, a negative electrode of the direct-current power supply 34 is electrically connected to the transparent electrode film 14 and a positive electrode of the direct-current power supply 34 is electrically connected to the electrode film 24 .
  • the transparent electrode film 14 and the electrode film 24 can form a short circuit via a circuit (not shown).
  • H + is a hydrogen ion
  • e ⁇ is an electron
  • Tungsten trioxide which is the material of the electrochromic film 16 is colored.
  • light (see the arrow shown in FIG. 1 ) which enters the glass substrate 12 from the surface side of the glass substrate 12 and is reflected by the light reflecting film 18 passes through the colored electrochromic film 16 , and the amount of the light is reduced. Therefore, the reflectivity of the electrochromic film 10 is changed to exhibit glare-proofing effect.
  • the electrochromic mirror 10 has a simple structure in which the transparent electrode film 14 , the electrochromic film 16 and light reflecting film 18 (only three films) are formed on the glass substrate 12 .
  • the film thickness and the film quality or the like of the transparent electrode film 14 , the electrochromic film 16 and the light reflecting film 18 do not easily influence performance. Therefore, the electrochromic mirror is easily manufactured at a low cost.
  • the electrochromic film 16 is formed between the transparent electrode film 14 to which a negative voltage is applied and the light reflecting film 18 . Since the electrochromic film 16 is formed between the transparent electrode film 14 to which a negative voltage is applied and the light reflecting film 18 , hydrogen ions are compulsorily drawn into the electrochromic film 16 . As a result, the response of the reduction coloring of the electrochromic film 16 is improved.
  • the electrochromic mirror 10 can be easily manufactured at a low cost. In addition, no double images occur, and the electrochromic mirror has a simple structure and high performance.
  • sulfuric acid is used as a hydrogen ion agent contained in the electrolytic solution 28 , but the invention is not limited thereto.
  • a general acid can be used as the hydrogen ion agent contained in the electrolytic solution 28 , and examples of the acid include hydrochloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid and perchloric acid.
  • ferrocene (Fe(C 5 H 5 ) 2 ) used as neutral molecules (neutral material) contained in the electrolytic solution 28 is a compound containing iron, but the invention is not limited thereto.
  • a compound which is generally called metallocene can be used as neutral molecules (neutral material) contained in the electrolytic solution 28 .
  • an electrochromic mirror 50 of the second embodiment has the same structure as that of the electrochromic mirror 10 of the first embodiment, except that an electrolytic solution is different from that of the first embodiment.
  • a solvent of the electrolytic solution 52 of the electrochromic mirror 50 is propylene carbonate, and the electrolytic solution 52 contains lithium perchlorate (LiClO 4 ) as a lithium ion agent and ferrocene (Fe(C 5 H 5 ) 2 ) which is a neutral material as a redox agent.
  • Li + is a lithium ion and e ⁇ is an electron.
  • oxidation reaction which is the same as the formula (12) in the first embodiment occurs near the electrode film 24 in the electrolytic solution 52 .
  • Tungsten trioxide which is the material of the electrochromic film 16 is colored.
  • light (see the arrow shown in FIG. 1 ) which enters the glass substrate 12 from the surface side of the glass substrate 12 and is reflected by the light reflecting film 18 passes through the colored electrochromic film 16 , and the amount of the light is reduced. Therefore, the reflectivity of the electrochromic film 10 is changed to exhibit glare-proofing effect.
  • lithium perchlorate (LiClO 4 ) is used as a lithium ion agent contained in the electrolytic solution 52 , but the invention is not limited thereto.
  • the lithium ion agent contained in the electrolytic solution 52 include lithium salts such as lithium tetrafluoroborate (LiBF 4 ) and lithium hexafluoroarsenate (LiAsF 6 ).
  • an electrochromic mirror 60 of the third embodiment has the same structure as that of the electrochromic mirror 10 of the first embodiment, except that an electrolytic solution is different from that of the first embodiment.
  • a solvent of the electrolytic solution 62 of the electrochromic mirror 60 is propylene carbonate, and the electrolytic solution 62 contains ferrocyanic acid (H 4 [Fe(CN) 6 ])as an electrolyte.
  • Tungsten trioxide (WO 3 ) which is the material of the electrochromic film 16 is colored.
  • light see the arrow shown in FIG. 1
  • the reflectivity of the electrochromic film 50 is changed to exhibit glare-proofing effect.
  • an electrochromic mirror 70 of the fourth embodiment has the same structure as that of the electrochromic mirror 10 of the first embodiment, except that an electrolytic solution is different from that of the first embodiment.
  • the solvent of the electrolytic solution 72 of the electrochromic mirror 70 is water
  • the electrolytic solution 62 contains potassium ferrocyanide (K 4 [Fe(CN) 6 ]) as an electrolyte.
  • hydrogen ions contained in water are used as hydrogen ions contained in the electrolytic solution 72 .
  • Tungsten trioxide which is the material of the electrochromic film 16 is colored.
  • Potassium ions (K + ) and hydroxyl ions (OH ⁇ ) which are not described in the formula (18) are not changed.
  • each of the electrolytic solutions 28 , 52 , 62 and 72 contains a polymer or an inorganic substance which is nonreactive with the electrolytic solution and is gelled.
  • Examples of the polymer include an acrylic resin, and examples of the inorganic substance include silica.
  • a platinum group noble metal such as platinum, rhodium, palladium, or an alloy including any of these metals (for instance, an alloy of silver and a platinum-group metal or the like) is preferable as the material of the light reflecting film.
  • the platinum group noble metal makes hydrogen molecules hydrogen atoms due to its catalyst operation and holds the hydrogen atoms, and the hydrogen atoms easily permeates the light reflecting film.
  • the platinum group noble metal absorbs hydrogen in the electrochromic film and returns the hydrogen to the electrolytic solution when application of voltages is stopped.
  • the light reflecting film is preferably made of rhodium since lithium atoms permeates a rhodium film very well.
  • the transparent electrode film include a so-called “ITO film” made of a mixture of indium oxide and tin oxide, a so-called “FTO film” in which fluorine is doped in tin oxide, or a so-called “ATO film” in which antimony is doped in tin oxide.
  • a metal plate having conductivity or the like can be used as the (support) substrate of the electrochromic mirror, a material having a thermal expansion coefficient approximate to that of the transparent substrate is preferable as the material of the support substrate. Therefore, a thin film (electrode film) having conductivity such as a metal film and a transparent conductive film is preferably formed on the surface of the substrate made of the same material (for instance, a glass and a plastic resin or the like) as the transparent substrate, and used as a conductive part.
  • tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ) and a mixture containing at least one of tungsten trioxide and molybdenum trioxide is preferable.

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  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
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  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
US10/867,778 2003-06-18 2004-06-16 Electrochromic mirror having variable reflectivity Expired - Lifetime US7088490B2 (en)

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JP2003173101 2003-06-18
JP2003-173101 2003-06-18
JP2004056387A JP4098736B2 (ja) 2003-06-18 2004-03-01 エレクトロクロミックミラー
JP2004-056387 2004-03-01

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US20050237591A1 (en) * 2004-04-22 2005-10-27 Kabushiki Kaisha Tokai-Rika-Denki-Seisakusho Variable reflectance mirror
US20070159316A1 (en) * 2005-11-23 2007-07-12 Electric Mirror, Llc Back lit mirror with media display device
US20080030835A1 (en) * 1999-05-14 2008-02-07 Tonar William L Electrochromic rearview mirror incorporating a third surface reflector
US20090002800A1 (en) * 2007-06-26 2009-01-01 Kabushiki Kaisha Tokai-Rika-Denki-Seisakubusho Electrochromic mirror
US20090185256A1 (en) * 2008-01-23 2009-07-23 Kabushiki Kaisha Tokai-Rika-Denki-Seisakusho Electrochromic mirror
US20090257140A1 (en) * 2005-11-23 2009-10-15 Electric Mirror, L.L.C. Mounting structure for a mirror assembly
US9576694B2 (en) 2010-09-17 2017-02-21 Drexel University Applications for alliform carbon
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JP4544903B2 (ja) 2004-04-26 2010-09-15 株式会社東海理化電機製作所 エレクトロクロミックミラー
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JP2006337635A (ja) * 2005-06-01 2006-12-14 Bridgestone Corp フォトエレクトロクロミック素子、並びに調光ガラス、透過率調整ガラス、熱線カットガラス及び画像表示デバイス
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JP2009008749A (ja) * 2007-06-26 2009-01-15 Tokai Rika Co Ltd エレクトロクロミックミラー
JP2009008751A (ja) * 2007-06-26 2009-01-15 Tokai Rika Co Ltd エレクトロクロミックミラー
JP4949136B2 (ja) * 2007-06-26 2012-06-06 株式会社東海理化電機製作所 エレクトロクロミックミラー
JP2009008750A (ja) * 2007-06-26 2009-01-15 Tokai Rika Co Ltd エレクトロクロミックミラー
JP2010139541A (ja) * 2008-12-09 2010-06-24 Konica Minolta Holdings Inc 表示素子
US9215831B2 (en) * 2012-11-22 2015-12-15 Huawei Technologies Co., Ltd. Heat dissipation system
JP2021021872A (ja) * 2019-07-30 2021-02-18 株式会社リコー エレクトロクロミック装置、光学レンズデバイス、眼鏡、エレクトロクロミック装置の制御装置、エレクトロクロミック装置の制御方法、及び、エレクトロクロミック装置の制御プログラム

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US20090185256A1 (en) * 2008-01-23 2009-07-23 Kabushiki Kaisha Tokai-Rika-Denki-Seisakusho Electrochromic mirror
US7903314B2 (en) * 2008-01-23 2011-03-08 Kabushiki Kaisha Tokai-Rika-Denki-Seisakusho Electrochromic mirror
US9752932B2 (en) 2010-03-10 2017-09-05 Drexel University Tunable electro-optic filter stack
US9576694B2 (en) 2010-09-17 2017-02-21 Drexel University Applications for alliform carbon
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EP1488957B1 (fr) 2011-03-23
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JP2005031628A (ja) 2005-02-03
EP1488957A1 (fr) 2004-12-22

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